Fluorine-free organosilicon polymer with impermeability and application thereof

Abstract

The invention aims to provide a fluoride-free organosilicon polymer with impermeability and application thereof. The fiber treating agent prepared from the organosilicon polymer can endow fibers with the capability of preventing water-based and oil-based liquid from permeating, and meanwhile, the original appearance and hand feeling of the fibers are kept. The organosilicon polymer provided by the invention comprises a repeating unit formed by polymerizing the following monomers: a siloxane monomer I containing a carbon-carbon double bond, a monomer II with a hydrophilic functional group and a crosslinking site, an acrylate or methacrylate monomer III with the glass transition temperature lower than 10 DEG C, a cationic monomer IV containing a tertiary amine group and a monomer V selected from halogenated alkane.

Description

Technical Field

[0001] The present invention relates to a fluorine-free organosilicon polymer with anti-permeability performance and application thereof in fiber treatment, in particular to an organosilicon polymer for treating natural fibers and synthetic fibers and a fiber treating agent containing the polymer. Background Art

[0002] In recent years, with the increasing demand for material functionality, surface treatment technology has received widespread attention. Imparting surface impermeability to objects is particularly important, as this property effectively protects them from water and oil stains, extending their service life.

[0003] Traditional fluorinated compounds possess excellent oil and water repellency. For example, CN103080267A proposes using polymers formed from fluorinated acrylates and other monomers to impart water and oil resistance to textiles. However, due to potential threats to the environment and human health, the use of fluorocarbon polymers has been increasingly restricted. Therefore, the development of novel fluorine-free polymers with excellent protective properties has become an urgent need for both industry and society.

[0004] Silicone polymers, due to their excellent weather resistance, chemical inertness, thermal stability, and low surface energy, have become a popular alternative to fluoropolymers and are widely used in surface treatment applications. CN107353821A discloses a two-component silicone coating that imparts excellent water resistance to leather, but lacks oil resistance.

[0005] Therefore, developing a fluorine-free silicone polymer with anti-permeation properties to meet the needs of surface treatment of various articles is a technical challenge faced by those skilled in the art. Summary of the Invention

[0006] In view of the above problems existing in the prior art, the present invention provides a fluorine-free silicone polymer with anti-permeability and its application. The silicone polymer or the fiber treatment agent obtained from the silicone polymer can be used for the surface treatment of fiber materials to impart anti-permeability to the surface of the article.

[0007] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0008] An organosilicon polymer, comprising a repeating unit generated from monomer I, a repeating unit generated from monomer II, a repeating unit generated from monomer III, a repeating unit generated from monomer IV, and a repeating unit generated from monomer V:

[0009] The general structural formula of monomer I is as follows:

[0010]

[0011] Wherein, R1 is H or an alkyl group having 1 to 10 carbon atoms; 0≤n≤20;

[0012] X is independently one or more of an alkylene group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an amino group, an amide group, or an acyloxy group;

[0013] Y is selected from the following structures:

[0014]

[0015] wherein R2 and R3 are independently a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R4 is a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms or a silyl group; 0≤c≤20, 0≤m≤10, and d is one of 0, 1, and 2;

[0016] L is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a silyl group, or the following structure:

[0017]

[0018] Among them, R5 and R6 are independently a linear, branched or cyclic alkyl group with 1 to 20 carbon atoms or an aryl group with 6 to 20 carbon atoms, and R7, R8 and R9 are independently a linear, branched or cyclic alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 10 carbon atoms or a silyl group; 0≤e≤20.

[0019] Monomer II is selected from one or more polymerizable unsaturated monomers containing functional groups, wherein the functional groups include one or more of carboxyl groups, sulfonic acid groups, hydroxyl groups, amino groups, ether groups, and epoxy groups.

[0020] Monomer III is selected from acrylate monomers or methacrylate monomers having a glass transition temperature of less than 10° C., and is preferably an alkyl (meth)acrylate having an alkyl group having 1 to 20 carbon atoms, preferably 4 to 15 carbon atoms.

[0021] The general structural formula of monomer IV is as follows:

[0022]

[0023] Where, Q is N or O; R 10 is H or an alkyl group with 1 to 10 carbon atoms; R 11 and R 12 Each is independently a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; 0≤f≤20.

[0024] Monomer V is a halogenated alkane having a long-chain alkyl group, and the halogenated alkane is preferably a chlorinated alkane or a brominated alkane.

[0025] The organosilicon polymer obtained by the present invention improves the anti-permeation effect by providing low surface energy through the introduction of organosilicon of monomer I.

[0026] According to some embodiments of the polymer of the present invention, the mass content of the repeating unit generated by monomer I, the repeating unit generated by monomer II, the repeating unit generated by monomer III, the repeating unit generated by monomer IV, and the repeating unit generated by monomer V is 30-80%: 10-60%: 1-30%: 1-20%: 1-20%.

[0027] According to some embodiments of the polymer of the present invention, R1 in monomer I is preferably H or methyl.

[0028] According to some embodiments of the polymer of the present invention, the monomer I is selected from one or more of the following monomers:

[0029]

[0030] According to some embodiments of the polymer of the present invention, the molecular weight of the monomer I is selected to be 200 to 10,000, preferably 400 to 4,000.

[0031] According to some embodiments of the polymer of the present invention, monomer II is selected from one or more of acrylic acid, methacrylic acid, methylene succinic acid, styrene sulfonic acid, sodium vinyl sulfonate, acrylamidomethylpropanesulfonic acid, glycidyl acrylate, glycidyl methacrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, acrylamide, and N-hydroxymethyl acrylamide.

[0032] The molecular weight of the polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate and methoxy polyethylene glycol (meth)acrylate is 200 to 2000, preferably 300 to 1000.

[0033] According to some embodiments of the polymer of the present invention, monomer III is selected from one or more of ethyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, and n-octyl methacrylate.

[0034] According to some embodiments of the polymer of the present invention, R 10 Preferably it is H or methyl.

[0035] According to some embodiments of the polymer of the present invention, monomer IV is selected from one or more of dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, and diethylaminopropyl (meth)acrylamide.

[0036] According to some embodiments of the polymer of the present invention, the long-chain alkyl halogenated hydrocarbon described in monomer V refers to a chloroalkane or a bromoalkane with an alkyl chain length of not less than 8, such as one or more of 1-chlorodecane, 1-bromodecane, 1-chlorododecane, 1-bromododecane, 1-chlorotetradecane, 1-bromodetradecane, 1-chlorohexadecane, 1-bromohexadecane, 1-chlorooctadecane, 1-bromooctadecane, 1-bromooctadecane, 1-chlorodocosane, and 1-bromodocosane.

[0037] The present invention also relates to a method for preparing the organosilicon polymer.

[0038] In the present invention, the monomers are polymerized by free radicals to form copolymers.

[0039] Preferably, the free radical polymerization reaction is carried out in the presence of a free radical initiator, and the free radical initiator is one or more of an azo or peroxide initiator.

[0040] Preferably, the azo initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptanenitrile, and dimethyl azobisisobutyrate.

[0041] Preferably, the peroxide initiator is selected from one or more of benzoyl peroxide, dilauroyl peroxide, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, diisopropyl benzene peroxide, tert-butyl perbenzoate, tert-butyl pervalerate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, hydrogen peroxide, potassium persulfate, sodium persulfate, and ammonium persulfate.

[0042] In addition, the free radical polymerization reaction can also utilize a redox initiation system. Specifically, the initiators constituting the redox initiation system primarily include benzoyl peroxide / sucrose, tert-butyl hydroperoxide / rongalite, tert-butyl hydroperoxide / sodium metabisulfite, tert-butyl hydroperoxide / ferrous sulfate, benzoyl peroxide / N,N′-dimethylaniline, ammonium persulfate / sodium bisulfite, potassium persulfate / sodium bisulfite, cumene hydroperoxide / tetraethyleneimine, ammonium persulfate / ferrous sulfate, and potassium persulfate / ferrous chloride. Tert-butyl hydroperoxide / sodium metabisulfite is preferred.

[0043] According to some embodiments of the polymer of the present invention, the free radical polymerization temperature of the polymer is preferably 30 to 100° C., more preferably 40 to 80° C. In addition, the polymerization time is preferably 5 to 20 hours, more preferably 6 to 12 hours.

[0044] According to some embodiments of the polymer of the present invention, the weight average molecular weight of the polymer is 1,000 to 1,000,000, preferably 5,000 to 5,000,000. The molecular weight of the polymer can be adjusted by adding a chain transfer agent.

[0045] The present invention further provides a fiber treating agent comprising the above-mentioned organosilicon polymer of the present invention and a solvent, wherein the solvent comprises water and / or an organic solvent.

[0046] Specifically, the above-mentioned organic solvents are alcohols, ketones, ethers, amides or others that are partially or completely miscible with water.

[0047] Preferably, the alcohol is methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, or glycerol.

[0048] Preferably, the ketones are acetone, methyl ethyl ketone, or 4-methyl-2-pentanone.

[0049] Preferably, the ethers are diethyl ether and dibutyl ether.

[0050] Preferably, the esters are ethyl acetate, butyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate

[0051] Preferably, the amides are N,N-dimethylformamide, dimethylformamide

[0052] Preferably, the others are acetonitrile, dimethyl sulfoxide, or tetrahydrofuran.

[0053] The present invention also relates to a preparation process of the fiber treating agent, which specifically comprises the following steps:

[0054] A. In an organic solvent, monomer I, monomer II, monomer III and monomer IV are subjected to free radical polymerization in a certain proportion under inert protection conditions to obtain an organosilicon copolymer.

[0055] B. Adding monomer V to the organosilicon copolymer solution obtained in step A to react to obtain an organosilicon quaternary ammonium salt solution.

[0056] C. The organosilicon quaternary ammonium salt solution obtained in step B is adjusted to a pH close to neutral, and dispersed in water to obtain the fiber treating agent.

[0057] The fiber treatment agent of the present invention may contain deodorants, antioxidants, colorants, ultraviolet absorbers, light stabilizers, antistatic agents, plasticizers, flame retardants, thickeners, film-forming aids, organic solvents, other resins, etc., within a range that does not affect the effects of the present invention.

[0058] The present invention also provides the use of the above-mentioned organosilicon polymer or the above-mentioned treatment agent in a fiber substrate, which can be exemplified by natural fibers such as cotton, hemp, linen, wool, silk, cashmere, asbestos, and chemical fibers such as polyamide, polyester, viscose, cellulose, and glass. Fiber processed products include all kinds of paper products, fabrics, non-woven fabrics, or films. As a drying method, it is preferred to place the product at room temperature for 10 minutes to several dozen hours or to dry it at a temperature of 20 to 150°C for 0.5 minutes to 5 hours.

[0059] The method for coating the organosilicon polymer of the present invention or the above-mentioned fiber treatment agent on the fiber is not particularly limited. Examples include coating methods based on various coating machines such as gravure coaters, rod coaters, blade coaters, roll coaters, air knife coaters, screen coaters, curtain coaters, and brush coaters, spraying, dipping, etc., or directly adding during the material production process to the surface or interior of the material to impart oil and water penetration resistance.

[0060] The amount of the fiber treatment agent of the present invention attached to the fiber is not particularly limited, but is preferably 1 to 300 g / m 2 More preferably, 10 to 200 g / m 2 range to form.

[0061] Beneficial effects:

[0062] The organosilicon polymer and fiber treatment agent provided by the present invention can construct a durable protective layer on the fiber surface, significantly blocking the penetration of aqueous and oily liquids while giving the material reliable antibacterial and mildew-proof functions.

[0063] Monomer I is a low surface energy silicone monomer that can significantly reduce the surface tension of the fiber and provide water and oil repellency;

[0064] The hydrophilic functional groups and potential cross-linking sites introduced by monomer II give the polymer good water solubility and dispersibility to ensure sufficient wetting of the fiber; and after curing, it forms a dense network, improving long-term water and oil resistance.

[0065] Monomer III introduces a flexible segment to reduce the curing temperature, promote film formation, and keep the fiber soft;

[0066] Monomer IV is a cationic monomer that forms a strong and stable bond with the fiber through electrostatic interaction, improving wash fastness;

[0067] Monomer V is used to construct a quaternary ammonium salt structure, providing long-lasting antibacterial and anti-mildew protection for the fiber. BRIEF DESCRIPTION OF THE DRAWINGS

[0068] Figure 1 This is the performance of paper treated with the fiber treating agent according to an embodiment of the present invention in terms of liquid penetration resistance. DETAILED DESCRIPTION

[0069] In order to facilitate understanding by those skilled in the art, the present invention will be further described below with reference to the embodiments. The contents mentioned in the embodiments are not intended to limit the present invention.

[0070] Example 1

[0071] First, weigh 16 g of organosilicon monomer I-3 (average molecular weight 1250), 4 g of lauryl methacrylate, 6.5 g of methoxypolyethylene glycol (meth)acrylate (average molecular weight 300), 3.75 g of dimethylaminopropyl (meth)acrylamide, 0.375 g of 2-hydroxyethyl methacrylate, and 0.375 g of glycidyl methacrylate. Dissolve the mixed monomers in 30 g of isopropyl alcohol and stir thoroughly until transparent and uniform. Pour the monomer solution into a 250 ml three-necked flask, maintain thorough stirring, and purge with nitrogen for 5 minutes. After heating to 70°C and stabilizing, add 0.1 g of AIBN to initiate the reaction. After reacting for 4 hours, add another 0.1 g of AIBN and continue heating for another 4 hours. Next, add 3.96 g of 1-bromodecane and stir the mixture at 70°C overnight. Add glacial acetic acid to adjust the pH to 6-8, and slowly add deionized water equal to the amount of isopropyl alcohol. After the addition was complete, the temperature was raised to 81° C. to distill off the isopropyl alcohol, and deionized water in an amount equal to the original isopropyl alcohol was quickly added dropwise to obtain the fiber treatment agent with a solid content of 25%.

[0072] Example 2

[0073] First, weigh 16 grams of organosilicon monomer I-6, 4 grams of lauryl methacrylate, 6.5 grams of methoxypolyethylene glycol (meth)acrylate (average molecular weight 300), 3.75 grams of dimethylaminopropyl (meth)acrylamide, 0.375 grams of 2-hydroxyethyl methacrylate, and 0.375 grams of glycidyl methacrylate. Dissolve the mixed monomers in 30 grams of isopropyl alcohol and stir thoroughly until transparent and uniform. Pour the monomer solution into a 250 ml three-necked flask, maintain thorough stirring, and purge with nitrogen for 5 minutes. After heating to 70°C and stabilizing, add 0.1 grams of AIBN to initiate the reaction. After reacting for 4 hours, add another 0.1 grams of AIBN and continue heating for another 4 hours. Next, add 3.96 grams of 1-bromodecane and stir the mixture at 70°C overnight. Add glacial acetic acid to adjust the pH to 6-8, and slowly add deionized water equal to the amount of isopropyl alcohol. After the addition was complete, the temperature was raised to 81° C. to distill off the isopropyl alcohol, and deionized water in an amount equal to the original isopropyl alcohol was quickly added dropwise to obtain the fiber treatment agent with a solid content of 25%.

[0074] Example 3

[0075] First, weigh 16 g of organosilicon monomer I-9 (average molecular weight 1000), 4 g of lauryl methacrylate, 6.5 g of methoxypolyethylene glycol (meth)acrylate (average molecular weight 300), 3.75 g of dimethylaminopropyl (meth)acrylamide, 0.375 g of 2-hydroxyethyl methacrylate, and 0.375 g of glycidyl methacrylate. Dissolve the mixed monomers in 30 g of isopropyl alcohol and stir thoroughly until transparent and homogeneous. Pour the monomer solution into a 250 ml three-necked flask, maintain thorough stirring, and purge with nitrogen for 5 minutes. After heating to 70°C and stabilizing, add 0.1 g of AIBN to initiate the reaction. After reacting for 4 hours, add another 0.1 g of AIBN and continue heating for another 4 hours. Next, add 3.96 g of 1-bromodecane and stir the mixture at 70°C overnight. Add glacial acetic acid to adjust the pH to 6-8, and slowly add deionized water equal to the amount of isopropyl alcohol. After the addition was complete, the temperature was raised to 81° C. to distill off the isopropyl alcohol, and deionized water in an amount equal to the original isopropyl alcohol was quickly added dropwise to obtain the fiber treatment agent with a solid content of 25%.

[0076] Example 4

[0077] First, weigh 16 g of organosilicon monomer I-3 (average molecular weight 500), 4 g of lauryl methacrylate, 6.5 g of methoxypolyethylene glycol (meth)acrylate (average molecular weight 300), 3.75 g of dimethylaminopropyl (meth)acrylamide, 0.375 g of 2-hydroxyethyl methacrylate, and 0.375 g of glycidyl methacrylate. Dissolve the mixed monomers in 30 g of isopropyl alcohol and stir thoroughly until transparent and uniform. Pour the monomer solution into a 250 ml three-necked flask, maintain thorough stirring, and purge with nitrogen for 5 minutes. After heating to 70°C and stabilizing, add 0.1 g of AIBN to initiate the reaction. After reacting for 4 hours, add another 0.1 g of AIBN and continue heating for another 4 hours. Next, add 3.96 g of 1-bromodecane and stir the mixture at 70°C overnight. Add glacial acetic acid to adjust the pH to 6-8, and slowly add deionized water equal to the amount of isopropyl alcohol. After the addition was complete, the temperature was raised to 81° C. to distill off the isopropyl alcohol, and deionized water in an amount equal to the original isopropyl alcohol was quickly added dropwise to obtain the fiber treatment agent with a solid content of 25%.

[0078] Example 5

[0079] First, weigh 16 grams of organosilicon monomer I-3 (average molecular weight 1250), 4 grams of lauryl methacrylate, 6.5 grams of methoxypolyethylene glycol (meth)acrylate (average molecular weight 300), 3.75 grams of dimethylaminopropyl (meth)acrylamide, and 0.75 grams of 2-hydroxyethyl methacrylate. Dissolve the mixed monomers in 30 grams of isopropyl alcohol and stir thoroughly until transparent and uniform. Pour the monomer solution into a 250 ml three-necked flask, maintain stirring, and purge with nitrogen for 5 minutes. After heating to 70°C and stabilizing, add 0.1 grams of AIBN and allow to react. After 4 hours of reaction, add another 0.1 grams of AIBN and continue heating for another 4 hours. Next, add 3.96 grams of 1-bromodecane and stir the mixture at 70°C overnight. Add glacial acetic acid to the above solution to adjust the pH to 6-8, and slowly add deionized water equal to the amount of isopropyl alcohol. After the addition was complete, the temperature was raised to 81° C. to distill off the isopropyl alcohol, and deionized water in an amount equal to the original isopropyl alcohol was quickly added dropwise to obtain the fiber treatment agent with a solid content of 25%.

[0080] Example 6

[0081] First, weigh 16 grams of organosilicon monomer I-3 (average molecular weight 1250), 4 grams of lauryl methacrylate, 6.5 grams of methoxypolyethylene glycol (meth)acrylate (average molecular weight 600), 3.75 grams of dimethylaminopropyl (meth)acrylamide, 0.375 grams of 2-hydroxyethyl methacrylate, and 0.375 grams of glycidyl methacrylate. Dissolve the mixed monomers in 30 grams of isopropyl alcohol and stir thoroughly until transparent and uniform. Pour the monomer solution into a 250 ml three-necked flask, maintain thorough stirring, and purge with nitrogen for 5 minutes. After heating to 70°C and stabilizing, add 0.1 grams of AIBN to initiate the reaction. After reacting for 4 hours, add another 0.1 grams of AIBN and continue heating for another 4 hours. Next, add 3.96 grams of 1-bromodecane and stir the mixture at 70°C overnight. Add glacial acetic acid to adjust the pH to 6-8, and slowly add deionized water equal to the amount of isopropyl alcohol. After the addition was complete, the temperature was raised to 81° C. to distill off the isopropyl alcohol, and deionized water in an amount equal to the original isopropyl alcohol was quickly added dropwise to obtain the fiber treatment agent with a solid content of 25%.

[0082] Example 7

[0083] First, weigh 16 g of organosilicon monomer I-3 (average molecular weight 1250), 4 g of lauryl methacrylate, 3.75 g of dimethylaminopropyl (meth)acrylamide, 6.875 g of 2-hydroxyethyl methacrylate, and 0.375 g of glycidyl methacrylate. Dissolve the mixed monomers in 30 g of isopropyl alcohol and stir thoroughly until transparent and uniform. Pour the monomer solution into a 250 ml three-necked flask, maintain thorough stirring, and purge with nitrogen for 5 minutes. After stabilizing at 70°C, add 0.1 g of AIBN to initiate the reaction. After reacting for 4 hours, add another 0.1 g of AIBN and continue heating for another 4 hours. Next, add 3.96 g of 1-bromodecane and stir at 70°C overnight. Add glacial acetic acid to the solution to adjust the pH to 6-8. Slowly add deionized water in an amount equal to the isopropyl alcohol dropwise. After the addition is complete, heat the solution to 81°C to distill off the isopropyl alcohol. Simultaneously, add deionized water in an amount equal to the original amount of isopropyl alcohol dropwise. The fiber treating agent was obtained, and the solid content was 25%.

[0084] The applicant diluted the anti-permeation fiber treatment agent in the above embodiment of the present application with water to form a 1wt% solution, immersed ordinary filter paper in the diluted treatment agent, and then cured it at 120°C for 3 minutes, and then tested its anti-permeation performance according to the following standards.

[0085] Furthermore, the paper products treated with the above treatment agent not only have excellent anti-permeability effects, but also exhibit significant antibacterial and anti-mildew properties. To verify this property, the treated paper in the examples was selected and inoculated with bacteria and mold for antibacterial and anti-mildew testing.

[0086] Table 1 Waterproofness evaluation criteria:

[0087] Waterproof grade state 5 No surface wetting 4 Slightly moistened surface 3 Partial surface wetting 2 Surface wetting 1 Full surface wetting

[0088] Table 2 Oil resistance evaluation criteria:

[0089]

[0090] After being treated with the treating agents of Examples 1 to 7, the oil and water penetration resistance and antibacterial and anti-mildew properties of the paper were evaluated.

[0091] Table 3 Performance test results of the embodiment

[0092]

[0093]

[0094] It can be seen from the test results in the above table that the organosilicon polymer and the fiber treatment agent containing the polymer in the present invention have excellent anti-penetration performance and antibacterial and anti-mildew performance.

[0095] Compared with Example 4, Example 1 uses a monomer I with a higher molecular weight, which improves the water contact angle and has better hydrophobicity.

[0096] Compared with Example 5, Example 1 introduces glycidyl methacrylate in monomer II to provide a denser cross-linked network, showing a higher water and oil repellency grade.

[0097] Compared with Example 6, the molecular weight of the methoxy polyethylene glycol (meth)acrylate in Monomer II in Example 1 is lower, and it exhibits a higher water and oil repellency rating;

[0098] Compared with Example 7, Example 1 introduces methoxy polyethylene glycol (meth)acrylate in monomer II, which shows better water dispersibility and higher water and oil repellency.

[0099] Figure 1 This paper demonstrates the liquid penetration resistance of paper treated with the fiber treatment agent of the present invention. By applying the organosilicon polymer and fiber treatment agent containing the polymer of the present invention, the liquid penetration resistance of the fiber material is enhanced. Specifically, the treated fiber material effectively prevents liquid penetration upon contact with liquid, thereby maintaining its structural and functional integrity.

[0100] The examples described above are merely illustrative and serve to illustrate some of the features of the method of the present invention. The appended claims are intended to claim the widest possible scope that can be envisioned, and the embodiments presented herein are merely illustrative of selected implementations according to a combination of all possible embodiments. Therefore, it is the applicant's intention that the appended claims are not limited by the selection of examples illustrating the features of the present invention. Some numerical ranges used in the claims also include subranges therein, and variations in these ranges should also be interpreted as being covered by the appended claims where possible.

Claims

1. A fluorine-free silicone polymer with anti-permeability performance, characterized in that: Contains the following repeating units: The repeating unit produced by monomer I has the following general structure: Wherein, R1 is selected from H or an alkyl group having 1 to 10 carbon atoms; 0≤n≤20; X is independently one or more of an alkylene group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an amino group, an amide group, or an acyloxy group; Y is selected from the following structures: wherein R2 and R3 are independently a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R4 is a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms or a silyl group; 0≤c≤20, 0≤m≤10, and d is one of 0, 1, and 2; L is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a silyl group, or the following structure: wherein R5 and R6 are independently a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R7, R8, and R9 are independently a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, or a silyl group; 0≤e≤20; The repeating unit produced by monomer II, monomer II is selected from one or more polymerizable unsaturated monomers containing functional groups, wherein the functional groups include one or more of carboxyl groups, sulfonic acid groups, hydroxyl groups, amino groups, ether groups, and epoxy groups; a repeating unit produced by monomer III, wherein monomer III is selected from an acrylate monomer or a methacrylate monomer having a glass transition temperature below 10°C; The repeating unit produced by monomer IV has the following general structure: Where, Q is N or O; R 10 is H or an alkyl group with 1 to 10 carbon atoms; R 11 and R 12 Each of the following is independently a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; 0≤f≤20; The repeating unit produced by monomer V is selected from a haloalkane having a long chain alkyl group, wherein the haloalkane is selected from a chloroalkane or a brominated alkane.

2. The organosilicon polymer according to claim 1, characterized in that The mass content ratio of the repeating unit generated by monomer I, the repeating unit generated by monomer II, the repeating unit generated by monomer III, the repeating unit generated by monomer IV, and the repeating unit generated by monomer V is 30-80%: 10-60%: 1-30%: 1-20%: 1-20%.

3. The organosilicon polymer according to claim 1, characterized in that R1 and R 10 Selected from H or methyl.

4. The organosilicon polymer according to claim 1, wherein The monomer I is selected from one or more of the following structures: The molecular weight of the monomer I is selected to be 200 to 10,000.

5. The organosilicon polymer according to claim 1, wherein The monomer II is selected from one or more of acrylic acid, methacrylic acid, methylene succinic acid, styrene sulfonic acid, sodium vinyl sulfonate, acrylamidomethylpropanesulfonic acid, glycidyl acrylate, glycidyl methacrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, acrylamide, and N-hydroxymethyl acrylamide; The molecular weight of the polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and methoxy polyethylene glycol (meth) acrylate is selected to be 200 to 2000; The monomer III is selected from one or more of ethyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, and n-octyl methacrylate; The monomer IV is selected from one or more of dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, and diethylaminopropyl (meth)acrylamide; The monomer V is selected from chloroalkanes or bromoalkanes with an alkyl chain length of not less than 8, specifically one or more of 1-chlorodecane, 1-bromodecane, 1-chlorododecane, 1-bromododecane, 1-chlorotetradecane, 1-bromodetradecane, 1-chlorohexadecane, 1-bromohexadecane, 1-chlorooctadecane, 1-bromooctadecane, 1-bromooctadecane, 1-chlorodocosane, and 1-bromodocosane.

6. A fiber treating agent, characterized in that The method comprises the organosilicon polymer according to any one of claims 1 to 5 and a solvent, wherein the solvent comprises water and / or an organic solvent.

7. The fiber treating agent according to claim 6, characterized in that The organic solvent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, glycerol, acetone, methyl ethyl ketone, 4-methyl-2-pentanone, ethyl ether, dibutyl ether, ethyl acetate, butyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, N,N-dimethylformamide, dimethylformamide, acetonitrile, dimethyl sulfoxide, and tetrahydrofuran.

8. A method for preparing a fiber treating agent according to claim 6, characterized in that: The following steps are involved: A. In an organic solvent, monomer I, monomer II, monomer III and monomer IV are subjected to free radical polymerization in a certain proportion under inert protection conditions to obtain an organosilicon copolymer; B. adding monomer V to the organosilicon copolymer solution obtained in step A to react to obtain an organosilicon quaternary ammonium salt solution; C. The organosilicon quaternary ammonium salt solution obtained in step B is adjusted to a pH close to neutral, and water is added to disperse the solution to obtain the fiber treating agent.

9. The preparation method according to claim 8, characterized in that The free radical polymerization reaction is carried out in the presence of a free radical initiator, and the free radical initiator is one or more of an azo or peroxide initiator; The free radical polymerization temperature is 30 to 100° C., and the polymerization time is 5 to 20 hours.

10. Use of the organosilicon polymer according to any one of claims 1 to 5, the fiber treating agent according to claim 7, or the treating agent prepared by the method according to claim 9 on a fiber substrate.

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